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NASA NTRS1978

Classification and generation of terrestrial rare gases

A Kr-84/Xe-130 versus Ne-20/Ar-36 diagram is a very useful format with which to study the elemental ratios of rare gases from terrestrial materials. It can separate not only the three types of rare gases which Ozima and Alexander (1976) classified but also the 'planetary' type rare gases from the other three types of rare gases. When all the available terrestrial rare gas data are plotted in a Kr-84/Xe-130 versus Ne-20/Ar-36 diagram, several observations can be made. First, most of the analyses of rare gases from shales yield Kr-84/Xe-130 ratios between the 'planetary' and atmospheric values. If, however, the atmosphere's high Kr-84/Xe-130 ratio was produced by the selective adsorption of xenon onto shales from an initially 'planetary' atmosphere, as is widely accepted, then the Kr-84/Xe-130 ratio in shales should be even lower than the 'planetary' value. Second, the rare gas pattern in the quenched rims of submarine basalts may be explained as fractionated samples of the rare gases in sea water.

Saito, K.↗

NASA NTRS1991

Noble gases in 'phase Q' - Closed-system etching of an Allende residue

Results are presented from an analysis, in nearly pure form, of noble gases from the 'phase-Q' in an HF/HCl residue of the Allende C3V meteorite, using the closed-system stepped etching technique developed by Wieler et al. (1986) and Benkert et al. (1988) to extract noble gases from the residue. The results yield precise values of element and isotope abundances of all five noble gases in phase-Q, which is the major carrier of the planetary gases in carbonaceous chondrites. It was found that Ne-Q and Xe-Q in Allende are very similar to trapped gases in ureilites and in oxidizable carriers in several classes of ordinary chandrites, indicating that Q-gases are present in the formation locations of all these meteorites.

Wieler, Rainer↗

NASA NTRS1991

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗

NASA NTRS1991

Source gases: Concentrations, emissions, and trends

Source gases are defined as those gases that influence levels of stratospheric ozone (O3) by transporting species containing halogen, hydrogen, and nitrogen to the stratosphere. Examples are the CFC's, methane (CH4), and nitrous oxide (N2O). Other source gases that also come under consideration in an atmospheric O3 context are those that are involved in the O3 or hydroxyl (OH) radical chemistry of the troposphere. Examples are CH4, carbon monoxide (CO), and nonmethane hydrocarbons (NMHC's). Most of the source gases, along with carbon dioxide (CO2) and water vapor (H2O), are climatically significant and thus affect stratospheric O3 levels by their influence on stratospheric temperatures. Carbonyl sulphide (COS) could affect stratospheric O3 through maintenance of the stratospheric sulphate aerosol layer, which may be involved in heterogeneous chlorine-catalyzed O3 destruction. The previous reviews of trends and emissions of source gases, either from the context of their influence on atmospheric O3 or global climate change, are updated. The current global abundances and concentration trends of the trace gases are given in tabular format.

Fraser, Paul J.↗

NASA NTRS1959

Halogen-Containing Gases as Boundary Lubricants for Corrosion-Resistant Alloys at 1200 F

The extreme temperatures anticipated for lubricated parts in advanced flight powerplants dictate the consideration of unconventional methods of lubrication such as solid lubricants and the reactive gases described in the present research. These halogen-containing "reactive" gases such as dichlorodifluoromethane, CF2Cl2, are among the most stable of organic molecules. The high "flash" temperatures generated at the contacting asperities as a result of frictional heat are sufficient to cause local decomposition of the halogen-containing gases. The active atoms thus released (e.g., chlorine) then react with the metal to be lubricated to form halides capable of effective lubrication. The presence of small amounts of a sulfur-containing gas (e.g., 1 percent sulfur hexafluoride, SF6) was found to catalyze the formation of metal halides. Friction and wear studies were made with a hemisphere (3/16-in. rad.) rider sliding in a circumferential path on the flat surface of a rotating disk (2 1/2-in. diam.). The specimens of corrosion-resistant 2 alloys were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 120 feet per minute, and temperature from 75 to 1200 F. An effective lubricant for ferritic materials (M-1 tool steel) was CF2Cl2, but significant corrosion occurred above 600 F. Corrosion evaluation in CF2Cl2 suggested a number of nickel- and cobalt-base alloys for additional lubrication study. Several combinations of gases and these metals were found to lubricate to 1200 F without excessive corrosion. The gases were CF2Cl2 Plus 1 percent SF6, monobromotrifluoromethane CF3Br plus 1 percent SF6, dibromodifluoromethane CF2Br2, iodotrifluoromethane, CF3I, and I2. Careful selection of metals and gas are necessary for successful lubrication over specific temperature ranges. Optimum combinations give friction coefficients as low as 0.05 without

Buckley, Donald H.↗

NASA NTRS1997

On the Relation between Stratospheric Chlorine/Bromine Loading and Short-Lived Tropospheric Source Gases

Current methods for estimating the concentrations of inorganic chlorine/bromine species Cl(y)/Br(y) in the stratosphere due to decomposition of tropospheric source gases assume that the Cl(y)/Br(y) concentration in the stratosphere is determined mainly by the balance between production from in situ oxidation of the source gases in the stratosphere and removal by transport of Cl(y)/Br(y) out of the stratosphere. The rationale being that for source gases whose lifetimes are of the order of several months or longer the concentration of Cl(y)/Br(y) in the troposphere is small because they are produced at a relatively slow rate and also removed efficiently by washout processes. As a result of the small concentration, the rate at which Cl(y)/Br(y) is transported to the stratosphere is expected to be small compared to the in situ stratospheric production. Thus the transport of Cl(y)/Br(y) from the troposphere contributes little to the stratospheric concentration. In contrast, the origin of stratospheric Cl(y)/Br(y) from reactive source gases with tropospheric lifetimes comparable to the washout lifetime of Cl(y)/Br(y) (of the order of 10-30 days) in the troposphere is distinctly different. The in situ source in the stratosphere is expected to be significantly smaller because only a small portion of the source gas is expected to survive the troposphere to be transported into this region. At the same time these short-lived source gases produce appreciable amounts of Cl(y)/Br(y) in the troposphere such that transport to the stratosphere offers a larger source for stratospheric Cl(y)/Br(y) than in situ production. Thus, for reactive source species, simple methods of estimating the concentration of stratospheric Cl(y)/Br(y) that ignore the tropospheric contribution will seriously underestimate the loading. Therefore estimation of the stratospheric Cl(y)/Br(y) loading requires not only measurements of tropospheric source gases but also measurements of Cl(y)/Br(y) at the tropopause. This paper illustrates the mechanism by using results from a two-dimensional chemistry-transport model. However, in view of the importance of tropospheric transport on stratospheric loading the detailed values should be further evaluated using a three-dimensional model with appropriate treatment of convective transport.

Ko, Malcolm K. W.↗

NASA NTRS2000

An abiotic origin for hydrocarbons in the Allan Hills 84001 martian meteorite through cooling of magmatic and impact-generated gases

Thermodynamic calculations of metastable equilibria were used to evaluate the potential for abiotic synthesis of aliphatic and polycyclic aromatic hydrocarbons (PAHs) in the martian meteorite Allan Hills (ALH) 84001. The calculations show that PAHs and normal alkanes could form metastably from CO, CO2, and H2 below approximately 250-300 degrees C during rapid cooling of trapped magmatic or impact-generated gases. Depending on temperature, bulk composition, and oxidation-reduction conditions, PAHs and normal alkanes can form simultaneously or separately. Moreover, PAHs can form at lower H/C ratios, higher CO/CO2 ratios, and higher temperatures than normal alkanes. Dry conditions with H/C ratios less than approximately 0.01-0.001 together with high CO/CO2 ratios also favor the formation of unalkylated PAHs. The observed abundance of PAHs, their low alkylation, and a variable but high aromatic to aliphatic ratio in ALH 84001 all correspond to low H/C and high CO/CO2 ratios in magmatic and impact gases and can be used to deduce spatial variations of these ratios. Some hydrocarbons could have been formed from trapped magmatic gases, especially if the cooling was fast enough to prevent reequilibration. We propose that subsequent impact heating(s) in ALH 84001 could have led to dissociation of ferrous carbonates to yield fine-grain magnetite, formation of a CO-rich local gas phase, reduction of water vapor to H2, reequilibration of the trapped magmatic gases, aromatization of hydrocarbons formed previously, and overprinting of the synthesis from magmatic gases, if any. Rapid cooling and high-temperature quenching of CO-, H2-rich impact gases could have led to magnetite-catalyzed hydrocarbon synthesis.

Non-NASA Center↗

NASA NTRS1994

Biomass Burning and the Production of Greenhouse Gases

Biomass burning is a source of greenhouse gases, carbon dioxide, methane, and nitrous oxide. In addition, biomass burning is a source of chemically active gases, including carbon monoxide, nonmethane hydrocarbons, and nitric oxide. These gases, along with methane, lead to the chemical production of tropospheric ozone (another greenhouse gas) as well as control the concentration of the hydroxyl radical, which regulates the lifetime of almost every atmospheric gas. Following biomass burning, biogenic emissions of nitrous oxide, nitric oxide, and methane are significantly enhanced. It is hypothesized that enhanced postburn biogenic emissions of these gases are related to fire-induced changes in soil chemistry and/or microbial ecology. Biomass burning, once believed to be a tropical phenomenon, has been demonstrated by satellite imagery to also be a regular feature of the world's boreal forests. One example of biomass burning is the extensive 1987 fire that destroyed more than 12 million acres of boreal forest in the People's Republic of China and across its border in the Soviet Union. Recent estimates indicate that almost all biomass burning is human-initiated and that it is increasing with time. With the formation of greenhouse and chemically active gases as direct combustion products and a longer-term enhancement of biogenic emissions of gases, biomass burning may be a significant driver for global change.

Levine, Joel S.↗

NASA NTRS2008

Mid-Infrared OPO for High Resolution Measurements of Trace Gases in the Mars Atmosphere

The Martian atmosphere is composed primarily (>95%) of CO2 and N2 gas, with CO, O2, CH4, and inert gases such as argon comprising most of the remainder. It is surprisingly dynamic with various processes driving changes in the distribution of CO2, dust, haze, clouds and water vapor on global scales in the meteorology of Mars atmosphere [I]. The trace gases and isotopic ratios in the atmosphere offer important but subtle clues as to the origins of the planet's atmosphere, hydrology, geology, and potential for biology. In the search for life on Mars, an important process is the ability of bacteria to metabolize inorganic substrates (H2, CO2 and rock) to derive energy and produce methane as a by-product of anaerobic metabolism. Trace gases have been measured in the Mars atmosphere from Earth, Mars orbit, and from the Mars surface. The concentration of water vapor and various carbon-based trace gases are observed in variable concentrations. Within the past decade multiple groups have reported detection of CH4, with concentrations in the 10's of ppb, using spectroscopic observations from Earth [2]. Passive spectrometers in the mid-infrared (MIR) are restricted to the sunlit side of the planet, generally in the mid latitudes, and have limited spectral and spatial resolution. To accurately map the global distribution and to locate areas of possibly higher concentrations of these gases such as plumes or vents requires an instrument with high sensitivity and fine spatial resolution that also has global coverage and can measure during both day and night. Our development goal is a new MIR lidar capable of measuring, on global scales, with sensitivity, resolution and precision needed to characterize the trace gases and isotopic ratios of the Martian atmosphere. An optical parametric oscillator operating in the MIR is well suited for this instrument. The sufficient wavelength tuning range of the OPO can extend the measurements to other organic molecules, CO2, atmospheric water vapor, clouds, temperature, dust, and aerosols, as well as possibly polar-cap properties. Our OPO-approach may allow a new capability for active remote sensing of the outer planets and moons, where the weaker sunlight further limit passive instruments. Here we report on the OPO development effort for this lidar instrument.

Yu, Anthony W.↗

NASA NTRS2018

Warming Early Mars by Impact Degassing of Reduced Greenhouse Gases

Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form collision induced absorptions (CIA) involving H2 and/or CH4 provide enough extra greenhouse power in a predominately CO2 atmosphere to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. Surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level for CIA to be effective. Atmospheres with 1-2 bars of CO2 and 2- 10% H2 can sustain surface environments favorable for liquid water. Smaller concentrations of H2 are sufficient if CH4 is also present. If thick CO2 atmospheres with percent level concentrations of reduced gases are the solution to the faint young Sun paradox for Mars, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks. In this paper we focus on impact delivered reduced gases.

Haberle, R. M.↗

DOE OSTI2025

Strain-Modulated Exciton Localization and Enhanced Emission in Multilayer GaSe

Strain engineering is one of the most effective routes for tuning the electrical and optical properties of two-dimensional layered materials. Besides reproducing the results of other groups on the tunability and photoluminescence (PL) enhancement of free and bound excitons under mechanical deformation or thermal effects, we systematically studied the mechanical strain (wrinkle) and local thermal strain (laser heating) effects on the PL lifetime and polarization in GaSe multilayers and their interplay, revealing their coupled impact on excitonic dynamics. Here, the PL intensity of localized excitons in the wrinkle region of GaSe increases superlinearly with the excitation laser power. The polarization effect has been observed for the bound exciton in GaSe under mechanical strain, but not in GaSe under thermal strain. Fluorescence lifetime imaging (FLIM) measurements reveal strain-tunable lifetimes for both free and bound excitons, and the lifetime of the bound exciton is longer than the free exciton in the mechanical strain region, correlating with the enhanced emission of the bound exciton. These results highlight previously uncharacterized optoelectronic tunability in GaSe and broaden the design space for strain (or thermally)-controlled 2D layered devices.

, GaSe, Exciton localization↗

NASA NTRS1974

Problem of nature of inert gases in lunar surface material

The origin of isotopes of inert gases in lunar surface material was investigated from the standpoint of the isotopic two-component status of inert gases in the solar system. Helium and neon represent the solar wind component, while krypton and xenon are planetary gases. Type A gases are trapped by the material of the regolith in the early stages of the existence of the solar system and were brought to the lunar surface together with dust. The material of the regolith therefore cannot be considered as the product of the erosion of the crystalline rocks of the moon and in this sense are extralunar. The regolith material containing type A gases must be identified with the high temperature minerals of the carbonaceous chondrites.

Levskiy, L. K.↗

NASA NTRS1977

Analytical methods for toxic gases from thermal degradation of polymers

Toxic gases evolved from the thermal oxidative degradation of synthetic or natural polymers in small laboratory chambers or in large scale fire tests are measured by several different analytical methods. Gas detector tubes are used for fast on-site detection of suspect toxic gases. The infrared spectroscopic method is an excellent qualitative and quantitative analysis for some toxic gases. Permanent gases such as carbon monoxide, carbon dioxide, methane and ethylene, can be quantitatively determined by gas chromatography. Highly toxic and corrosive gases such as nitrogen oxides, hydrogen cyanide, hydrogen fluoride, hydrogen chloride and sulfur dioxide should be passed into a scrubbing solution for subsequent analysis by either specific ion electrodes or spectrophotometric methods. Low-concentration toxic organic vapors can be concentrated in a cold trap and then analyzed by gas chromatography and mass spectrometry. The limitations of different methods are discussed.

Hsu, M.-T. S.↗

NASA NTRS1977

Effects of soil maturation on grain size-dependence of trapped solar gases

A description is presented of a simple two-part model which relates the retention of solar-wind-implanted noble gases and N in different grain sizes of lunar soils to the maturation level of that soil. It is assumed that concentrations of solar-wind gases are implanted into surfaces of soil grains in inverse proportion to grain diameter and that differences in irradiation probability and surface saturation as a function of grain diameter generally are not a major factor. The model demonstrates that incorporation of a major fraction of this surface-correlated gas into constructional particles such as agglutinates causes much of the gas to become volume-correlated in mature soils. This volume-correlated gas produces a relative enrichment in gas concentrations in coarser grains and a selective enrichment of more retentive gases (e.g., N) over less retentive gases (e.g., He). It is shown that the maturity model plays a major role in determining the complexities of the distribution of solar-wind gases in soils.

Bogard, D. D.↗

NASA NTRS1986

Studies of light noble gases in mineral grains from lunar soils: A status report

Among the lunar soil constituents, monomineralic grains deserve special attention. Noble gases of carefully prepared mineral separates from lunar bulk soils were studied. The major results and conclusions of these investigations are summarized, in the context of both the regolith evolution and the history of the solar corpuscular radiation. With regard to the most abundant noble gas component in the regolith samples (the solar gases) the mineral grains have mainly two properties giving these particles among all soil constituents the best characteristics as sensors for solar gases, despite the fact, that the noble gas concentrations in a mineral separate are 10 to 60 times lower that those in a bulk sample of the same grain size. The first of these properties is the mineral dependent retentivity of the light gases He and Ne, the second property concerns the relatively short time during which a mineral grain acquires it solar gases. These two points are briefly discussed.

Wieler, R.↗

NASA NTRS1985

The photochemistry of biogenic gases in the early and present atmosphere

The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.

Levine, J. S.↗

NASA NTRS1988

Use of propane as a quench gas in argon-filled proportional counters and comparison with other quench gases

An experimental investigation of propane and six other quench gases was carried out in argon-filled proportional counters. The objective of the study was to find the best gas mixture for optimizing the gas gain and the energy resolution as well as to understand the role of the ionization potential of quench gases in determining these parameters. It was found that the best gas gains and energy resolutions are obtained with propane, ethane, and isobutane in that order. The ionization potentials of these three lie below the argon metastable potentials and have the lowest value of resonance defect compared to the other quench gases. The better results obtained with these mixtures can be explained by an increased ionization yield resulting from the Penning effect. Propylene and trans-2-butene give inferior performance compared to the above three gases. Methane and carbon dioxide, the most commonly used quench gases in the argon-filled detectors, provide the worst results.

Agrawal, P. C.↗

NASA NTRS1993

Radiative interactions in molecular gases under local and nonlocal thermodynamic equilibrium conditions

Basic formulations, analyses, and numerical procedures are presented to investigate radiative heat interactions in diatomic and polyatomic gases under local and nonlocal thermodynamic equilibrium conditions. Essential governing equations are presented for both gray and nongray gases. Information is provided on absorption models, relaxation times, and transfer equations. Radiative flux equations are developed which are applicable under local and nonlocal thermodynamic equilibrium conditions. The problem is solved for fully developed laminar incompressible flows between two parallel plates under the boundary condition of a uniform surface heat flux. For specific applications, three diatomic and three polyatomic gases are considered. The results are obtained numerically by employing the method of variation of parameters. The results are compared under local and nonlocal thermodynamic equilibrium conditions at different temperature and pressure conditions. Both gray and nongray studies are conducted extensively for all molecular gases considered. The particular gases selected for this investigation are CO, NO, OH, CO2, H2O, and CH4. The temperature and pressure range considered are 300-2000 K and 0.1-10 atmosphere, respectively. In general, results demonstrate that the gray gas approximation overestimates the effect of radiative interaction for all conditions. The conditions of NLTE, however, result in underestimation of radiative interactions. The method developed for this study can be extended to solve complex problems of radiative heat transfer involving nonequilibrium phenomena.

Tiwari, S. N.↗